• Bulletin of the Korean Chemical Society
• /
• v.33 no.10
• /
• pp.3303-3310
• /
• 2012

Two single crystals of fully dehydrated partially $Li^+$-exchanged zeolite X were prepared by the exchange of Na-X, $Na_{92}Si_{100}Al_{92}O_{384}$ (Si/Al = 1.09), with $Li^+$ using aqueous 0.1 M $LiNO_3$ at 293 (crystal 1) and 333 K(crystal 2), followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. Their structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd{\overline{3}}$ at 100(1) K. Their structures were refined using all intensities to the final error indices (using the 1281 and 883 reflections for which ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2$ = 0.075/0.244 and 0.074/0.223 for crystals 1 and 2, respectively. Their compositions are seen to be ${\mid}Li_{86}Na_6{\mid}[Si_{100}Al_{92}O_{384}]$-FAU and ${\mid}Li_{87}Na_5{\mid}[Si_{100}Al_{92}O_{384}]$-FAU, respectively. In crystal 1, 17 $Li^+$ ions per unit cell are at site I', 15 another site I', 30 at site II, and the remaining 16 at site III; 2 $Na^+$ ions are at site II and the remaining 4 at site III'. In crystal 2, 32 and 30 $Li^+$ ions per unit cell fill sites I' and II, respectively, and the remaining 25 at site III'; 2 and 3 $Na^+$ ions are found at sites II and III', respectively. The extent of $Li^+$ exchange increases slightly with increasing ion exchange temperature from 93% to 95%.

• Korean Journal of Soil Science and Fertilizer
• /
• v.48 no.3
• /
• pp.180-188
• /
• 2015

To investigate the tendency of $Li^+$ exchange from polar organic solvents, $Li^+$-ion exchange into zeolite Y (Si/Al = 1.56) was attempted by undried methanol (crystal 1) and formamide (crystal 2) solvent. Two single crystals of Na-Y were treated with 0.1 M LiNO3 in each of the two solvents at 323 K, followed by vacuum dehydration at 723 K. Their structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd{\bar{3}}m$, at 100(1) K. In both structures, $Li^+$ for $Na^+$ ions filled preferentially sites I' and II. The remaining $Na^+$ ions occupied sites I', II, and III' in both structures, in additional to above sites, and $Na^+$ ions occupied site I in crystal 2. While the 68 % exchange of $Li^+$ for $Na^+$ was achieved from undried methanol, only 40 % exchange was observed from undried formamide, indicating that the undried methanol was more effective than undried formamide as solvent for $Li^+$ exchange under the conditions employed.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.1
• /
• pp.243-249
• /
• 2014

Three single crystals of fully dehydrated $Co^{2+}$-exchanged zeolite Y (Si/Al = 1.56) were prepared by the exchange of $Na_{75}$-Y ($|Na_{75}|[Si_{117}Al_{75}O_{384}]$-FAU) with aqueous streams 0.05 M in $Co(NO_3)_2$, pH = 5.1, at 294 K for 6 h, 12 h, and 18 h, respectively, followed by vacuum dehydration at 673 K. Their single-crystal structures were determined by synchrotron X-ray diffraction techniques in the cubic space group Fd3m at 100(1) K. They were refined to the final error indices $R_1/wR_2$ = 0.0437/0.1165, 0.0450/0.1228, and 0.0469/0.1278, respectively. Their unit-cell formulas are $|Co_{29.1}Na_{11.8}H_{5.0}|[Si_{117}Al_{75}O_{384}]$-FAU, $|Co_{29.8}Na_{11.0}H_{4.4}|[Si_{117}Al_{75}O_{384}]$-FAU, and $|Co_{30.3}Na_{9.5}H_{4.9}|[Si_{117}Al_{75}O_{384}]$-FAU, respectively. In all three crystals, $Co^{2+}$ ions occupy sites I, I' and II; $Na^+$ ions are also at site II. The tendency of $Co^{2+}$ exchange slightly increases with increasing contact time as $Na^+$ content and the unit cell constant of the zeolite framework decrease.

• Journal of the Korean Chemical Society
• /
• v.57 no.1
• /
• pp.12-19
• /
• 2013

The single-crystal structure of fully dehydrated partially $Li^+$-exchanged zeolite Y, ${\mid}Li_{50}Na_{25}{\mid}[Si_{117}Al_{75}O_{384}]$-FAU, was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 100(1) K. Ion exchange was accomplished by flowing stream of 0.1 M aqueous $LiNO_3$ for 2 days at 293 K, followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. The structure was refined using all intensities to the final error indices (using only the 801 reflections with ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2=0.043/0.140$. The 50 $Li^+$ ions per unit cell are found at three different crystallographic sites. The 19 $Li^+$ ions occupy at site I' in the sodalite cavity: the $Li^+$ ions are recessed 0.30 ${\AA}$ into the sodalite cavity from their 3-oxygens plane (Li-O = 1.926(5) ${\AA}$ and $O-Li-O=117.7(3)^{\circ}$). The 20 $Li^+$ ions are found at site II in the supercage, being recessed 0.23 ${\AA}$ into the supercage (Li-O = 2.038(5) ${\AA}$ and $O-Li-O=118.7(3)^{\circ}$). Site III' positions are occupied by 11 $Li^+$ ions: these $Li^+$ ions bind strongly to one oxygen atom (Li-O = 2.00(8) ${\AA}$). About 25 $Na^+$ ions per unit cell are found at four different crystallographic sites: 4 $Na^+$ ions are at site I, 5 at site I', 12 at site II, and the remaining 4 at site III'.

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.1
• /
• pp.41-50
• /
• 2022

To study the properties of Sr²⁺ exchange into zeolite A with increasing the molar concentration of Na⁺ in given exchange solution, four single crystals of fully dehydrated Sr²⁺- and Na⁺- exchanged zeolite A were prepared by the bath method using mixed ion-exchange solutions. The Sr(NO₃)₂:NaNO₃ molar rations of the ion exchange solution were 1:1(crystal 1), 1:100(crystal 2), 1:250(crystal 3), and 1:500 (crystal 4), respectively, with a total concentration of 0.05 M. The single-crystals were then vacuum dehydration at 623 K and 1×10^-4 Pa for 2 days. Their single-crystal structures were determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group Pm3-m, at 100(1) K, and were then refined to the final error indices of R₁/wR₂=0.047/0.146, 0.048/0.142, 0.036/0.128, and 0.040/0.156 for crystals 1, 2, 3, and 4, respectively. In crystals 1 and 2, the 6 Sr²⁺ ions are found at three different crystallographic sites. In crystal 3, 1 Sr²⁺ and 10 Na⁺ ions are found in large cavity and sodalite unit. In crystal 4, only 12 Na⁺ ions occupy three equipoints. The degree of Sr²⁺ ion-exchange decreased sharply from 100 to 16.7 to 0% as the initial Na⁺ concentration increase and the Sr²⁺ concentration decrease. In addition, the unit cell constant of the zeolite framework decreased with this lower level of Sr²⁺ exchange.